CN104628961A - Method for preparing polycarboxylate superplasticizer by carrying out graft copolymerization on acrylic ester polymer and fatty acid vinyl ester - Google Patents
Method for preparing polycarboxylate superplasticizer by carrying out graft copolymerization on acrylic ester polymer and fatty acid vinyl ester Download PDFInfo
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract
The invention relates to a method for preparing a polycarboxylate superplasticizer by carrying out graft copolymerization on acrylic ester polymer and fatty acid vinyl ester. According to the method for preparing the polycarboxylate superplasticizer by carrying out graft copolymerization on the acrylic ester polymer and fatty acid vinyl ester, acrylic ester polymer and fatty acid vinyl ester are taken as main reaction raw materials, polymerization is carried out firstly, then grafting is carried out and then alcoholysis and hydrolysis are carried out to prepare the polycarboxylate superplasticizer grafted and polymerized with the acrylic polymer and fatty acid vinyl ester, namely acrylic ester is taken as a reaction monomer, polymerization is carried out under the actions of an initiating agent and a molecular weight regulating agent, then graft polymerization is carried out with the fatty acid vinyl ester to obtain a graft copolymer with the acrylic ester polymer as a main chain and polyvinyl ester fatty acid as a side chain, and finally alcoholysis and hydrolysis are carried out on the graft copolymer. The method for preparing the polycarboxylate superplasticizer by carrying out graft copolymerization on the acrylic ester polymer and fatty acid vinyl ester has the advantages that a process is simple and easy to control, cost is low, environmental protection is realized, no pollution is produced, the fatty acid vinyl ester is used for replacing the existing polycarboxylate superplasticizer, and diversification of raw materials is enriched; and the prepared superplasticizer has good cement paste fluidity and holding capability and shows good cement adaptability and concrete application property.
Description
Technical field
The present invention relates to a kind of technical field of cement concrete polycarboxylate water-reducer, be related specifically to a kind of adopt the first autohemagglutination of acrylic ester monomer again with vinyl fatty ester generation graft copolymerization, eventually pass the concrete preparation method that alcoholysis and hydrolysis become the polycarboxylate water-reducer of pectination.
Background technology
In recent years, along with the develop rapidly of building industry, the consumption of concrete and cement constantly increases, cement additive has become one of requisite important component in building industry, the appearance of polycarboxylic acid polycarboxylate water-reducer, solve the problem of the low and slow setting of previous generation sulfonated lignin system ordinary water-reducing agent water-reducing rate, compensate for naphthalene water reducer contaminate environment and the fast shortcoming of loss of slump, because its water-reducing rate is high, function of slump protection is good, gain in strength is fast, the advantages such as suitability is strong, become the focus of concrete admixture research and development.But important polymeric monomer---the Soxylat A 25-7 of synthesis polycarboxylate water-reducer, its main raw material is oxyethane and propylene oxide, once raw material cut-off in the future, directly will have influence on the production of water reducer industry, so we must find can the new raw material of displaced loop oxidative ethane and propylene oxide, reduce the dependence to oxyethane and propylene oxide of water reducer industry, enrich the synthesizing mean of polycarboxylic acids dehydragent.
Along with the rise gradually of polymer ambit Middle molecule construction design method, the polymer molecular structure synthesizing ideal structure for us provides theoretical basis.We adopt more cheap and more various raw material by this polycarboxylate water-reducer of design, and synthetic product has the comb-type structure being similar to polycarboxylate water-reducer, ensures that it has good anchoring adsorptive power and space steric effect.This polymkeric substance not only has the various performances of traditional combed polycarboxylate water-reducer, also has cheapness simultaneously, does not rely on the advantage of epoxy second/propane, diversification of feedstock, have very wide using value.
Patent CN1712381 (publication date: on December 28th, 2005) reports a kind of preparation method of polyether grafting polyocarboxy acid type cement water reducing agent.This patent is that Zelan 338 sulfonation is obtained sulfonate styrene maleic anhydride copolymer by the sulfonated reagent not destroying anhydride group, then by itself and polyoxyethylene glycol hybrid reaction, water-solublely obtains polyether grafting polyocarboxy acid type cement water reducing agent.This invention has the advantages such as rational technology, simple to operate, reaction conditions is gentle, but the important composition of the raw material of this inventive method is ether, and raw material variety is more single, once raw material supply is restricted, will affect the production of water reducer to a great extent.
Patent CN1288870 (publication date: March 28 calendar year 2001) reports carboxylic-acid graft type polycarboxylate water-reducer and synthetic method thereof.The patent provides the synthetic method of two kinds of carboxylic acid type water reducing agents, one is become the poly carboxylic acid containing polyethoxye side base with acrylic acrylate class monomer polymerization again after reacting with maleic anhydride esterification with polyoxyethylene.Two is become containing carboxyl, hydroxyl, the multi-functional multipolymer of sulfonic group with the ethylenic unsaturation class monomer polymerization containing side base in redox system.This invention has that product performance are good, raw material is easy to get, and has the advantages such as good industrialization prospect.But the raw material polyoxyethylene in the first method of this invention is subject to the restriction of raw material equally, and the side chain of the water reducer synthesized in second method is very short, space steric effect can be poorer than the water reducer of long side chain, and the dissemination played cement granules can be poor.
The polyether macromonomer that patent CN103483504A reports two kinds of structures in (publication date on January 1st, 2014) combines the method preparing polycarboxylate water-reducer.This patent is to join in reactor by methacrylic Soxylat A 25-7, isopentenol polyoxyethylene ether, water, be uniformly mixed dissolving at 40 DEG C ~ 60 DEG C after, add vinylformic acid etc. again, add Thiovanic acid, be warming up to 75 DEG C ~ 85 DEG C, ammonium persulfate aqueous solution is added dropwise within the time of 70 ~ 90 minutes, at 75 DEG C ~ 85 DEG C, insulation carries out polyreaction in 2 ~ 3 hours again, then reacting rear material is cooled to room temperature, ph=6.8 ~ 7.2 are neutralized to, i.e. obtained polycarboxylate water-reducer with the aqueous sodium hydroxide solution of mass percent concentration 30%.This invention adopts polymeric monomer etc. to carry out combination copolymerization, synthesizes the polycarboxylate water-reducer of poly carboxylic acid, be conducive to the diminishing of existing polycarboxylate water-reducer product and guarantor collapse between balance and adjusting performance.But the ether of one of the important composition of this invention also can be subject to the restriction of raw material, can have influence on the production application of product.
The water reducer described in most patent has all possessed the serviceabilitys such as good mobility, dispersiveness.But, weak point to a certain degree is all had in above-mentioned preparation method, synthesis water reducer polymeric monomer used all needs oxyethane or propylene oxide to obtain, raw material variety is too single, once oxyethane and propylene oxide cut-off, the production of existing polycarboxylate water-reducer will certainly be subject to restriction to a certain extent, and then feeds through in Concrete Industry, and loss is difficult to estimate.So, this just requires the substitute finding oxyethane and propylene oxide as soon as possible, enrich the variation of raw material, and their coagulation efficiency and mechanisms in water reducer structure can be played, keep its excellent properties, can also ensure technological operation efficiently and cheap preparation cost simultaneously, be easy to suitability for industrialized production, relevant this respect work has no report both at home and abroad.
Summary of the invention
The object of this invention is to provide a kind of method that acrylic polymer graft copolymerization vinyl fatty ester prepares polycarboxylate water-reducer, adopt acrylate and vinyl fatty ester to be principal reaction raw material, prepare a kind of acrylic polymer graft copolymerization vinyl fatty ester class polycarboxylate water-reducer by the method for being first polymerized grafting more then alcoholysis and hydrolysis.The present invention is from design theory of molecular structure, is grafted to by vinyl fatty ester in polyacrylate backbone, forms a kind of structure being similar to pectination polycarboxylate water-reducer, thus plays water-reduction.The polycarboxylate water-reducer of present method synthesis is adopted to have good space steric effect, effectively can stop the disadvantageous effect that cement granules flocculates and hydrated cementitious produces mobility, cheapness simultaneously due to its raw material, shows the using value more excellent than traditional polycarboxylate water-reducer and development prospect.
The invention provides a kind of method that acrylic polymer graft copolymerization vinyl fatty ester prepares polycarboxylate water-reducer, it is characterized in that, by being first polymerized the method synthesis polycarboxylate water-reducer of alcoholysis and hydrolysis after grafting again, comprising following condition and step:
(1) polyreaction: first organic solvent is joined in reactor, be warming up to 60-130 DEG C, add molecular weight regulator, drip acrylate and the mixed solution 1-10 hour of initiator again, dropping terminates rear continuation isothermal reaction 0.5-5 hour, organic solvent is sloughed in underpressure distillation, obtains polymerisate polyacrylic ester;
(2) graft copolymerization: the polymerisate obtained in step (1) is joined in reactor, add water, emulsifying agent, molecular weight regulator successively again, be warming up to 50-95 DEG C, stir and treat that it mixes in 10-30 minute, then dropping vinyl fatty ester and massfraction are the initiator solution 1-10 hour of 5-50% respectively, dropping terminates rear continuation isothermal reaction 1-5 hour, be cooled to 25-40 DEG C, inorganic salt saturated solution breakdown of emulsion is added in the mixed emulsion obtained, use deionized water wash 2-5 time again, obtain polymerisate;
(3) alcoholysis reaction: the polymerisate obtained in step (2) is joined in alcoholic solvent, be warming up to 30-70 DEG C, add mineral alkali, alcoholysis 10-120 minute, after alcoholysis completes, alcoholic solvent and by product are sloughed in underpressure distillation, obtain polyacrylic ester-g-polyvinyl alcohol after drying;
(4) hydrolysis reaction: polymkeric substance step (3) obtained mixes with hydrolysis water used, be warming up to 30-70 DEG C, add mineral alkali, hydrolysis 10-120 minute, be hydrolyzed rear underpressure distillation and sloughed water solvent and by product, after drying, add the polycarboxylate water-reducer solution that aqueous solvent obtains desired concn;
Wherein, organic solvent used in the polyreaction described in step (1) is methyl alcohol, ethanol, p-Xylol, 200# solvent oil, ethylene glycol, toluene or hexanaphthene, and the mass ratio of consumption and acrylate is 2-10:1; Molecular weight regulator described in step (1) is Virahol, n-dodecyl mercaptan or the different monooctyl ester of 3-thiohydracrylic acid, and the mol ratio of consumption and acrylate is 0.001-0.05:1; Acrylate described in step (1) is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate or amyl acrylate; Initiator described in step (1) is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, tertbutyl peroxide, peroxidized t-butyl perbenzoate or di-t-butyl peroxide, and the mol ratio of consumption and acrylate is 0.001-0.05:1;
The consumption adding water described in step (2) and the polyacrylic ester mass ratio described in step (1) are 5-50:1; Emulsifying agent described in step (2) is sodium laurate, sodium laurylsulfonate, sodium lauryl sulphate or sodium stearate, and consumption is 0.00002-0.004:1 with the mol ratio adding water; Molecular weight regulator described in step (2) is n-dodecyl mercaptan, Virahol, Thiovanic acid or thiohydracrylic acid, and consumption and vinyl fatty ester mol ratio are 0.001-0.05:1; Vinyl fatty ester described in step (2) is vinyl-acetic ester, propionate or vinyl butyrate, and the mol ratio of consumption and the acrylate described in step (1) is 3-45:1; The solute of the initiator solution described in step (2) is Potassium Persulphate, Sodium Persulfate or ammonium persulphate, and the mol ratio of solute consumption and the acrylate described in step (1) is 0.1-0.2:1; Inorganic salt saturated solution described in step (2) is saturated nacl aqueous solution, saturated calcium chloride solution or saturated liquor alumini chloridi;
Alcohol described in step (3) is methyl alcohol, ethanol or propyl alcohol, and the mol ratio of consumption and the vinyl fatty ester described in step (2) is 2-5:1; Mineral alkali described in step (3) is sodium hydroxide or potassium hydroxide, and the mol ratio of consumption and alcohol is 0.001-0.01:1;
The consumption of the hydrolysis water used described in step (4) and the mol ratio of the acrylate described in step (1) are 2-10:1; Mineral alkali described in step (4) is sodium hydroxide or potassium hydroxide, and consumption is 0.001-0.01:1 with the mol ratio of hydrolysis water used.The inventive method compared with prior art has following beneficial effect:
1. the present invention is from design theory of molecular structure, pass through graft polymerization, formed with polyacrylic acid after alcoholysis and hydrolysis be main chain, the pectination polycarboxylate water-reducer that is side-chain structure with polyglycerol fatty acid vinyl acetate derivative, its similar is in traditional pectination polycarboxylate water-reducer, the innovation again on water reducer direction and breakthrough, for follow-up deep level development new variety polycarboxylate water-reducer has widened thinking and direction.
2. the polycarboxylate water-reducer of synthesis has the structure of pectination, and its poly carboxylic acid main chain is adsorbed on cement particle surface, and polyvinyl alcohol side chain plays good space steric effect, is preventing that cement cohesion, raising cement paste stability have good effect.This product is a kind of pectination polycarboxylate water-reducer with unique advantage, has good application prospect and the market competitiveness.
3. the synthetic method of this product is compared with traditional polycarboxylate water-reducer, desired raw material is more common is easy to get in reaction, be dirt cheap, whole reaction process is simply controlled, free radical solution polymerization used, graft polymerization, Alcoholysis Step are also normal operations technique, without the need to special operational and expensive reagent, to equipment and experimental situation without particular requirement, be easy to realize suitability for industrialized production.
4. this product preparation process energy consumption low, safety and environmental protection, mild condition, cleanliness without any pollution, nontoxic, synthetic method is simple, the vinyl fatty ester low price used, reduce the cost of product, enrich the diversity of raw material, break away from the dependency of water reducer industry to oxyethane and propylene oxide, improve product competitiveness and development prospect.
5. the polycarboxylate water-reducer of the present invention's synthesis has good workability, diminishing dispersive ability and guarantor and to collapse effect, just can show reasonable mobility and hold facility, and show very strong adaptability to the cement of different varieties compared with under low-dosage.In addition, this Product Status is stablized, and after leaving standstill under high density, not stratified, low temperature is non-crystallizable and performance is unaffected after storing.This synthetic method is while having the advantage such as simply direct, and the product of synthesis still has excellent property indices, is conducive to suitability for industrialized production, has good economic benefit and social benefit.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but enforcement of the present invention is not limited thereto.
Embodiment 1
First 200g methyl alcohol is joined in reactor, be warming up to 60 DEG C, add 3.489g Virahol, drip 100g methyl acrylate and the mixed solution of 0.288g 2,2'-Azobis(2,4-dimethylvaleronitrile) 10 hours again, dropping terminate rear continuation isothermal reaction after 0.5 hour underpressure distillation slough methyl alcohol, obtain polymerisate polymethyl acrylate.Getting the polymerisate polymethyl acrylate that 90g obtains joins in reactor, add 450g water again, 22.2g sodium laurate, 9.42g Virahol, be warming up to 50 DEG C, stir and treat that it mixes in 10 minutes, then the persulfate aqueous solution 10 hours that 357.96g vinyl butyrate and 567g massfraction are 5% is dripped respectively, dropping terminates rear continuation isothermal reaction 3 hours, be cooled to 25 DEG C, saturated nacl aqueous solution breakdown of emulsion is added in the mixed emulsion obtained, use deionized water wash again 2 times, obtain graft copolymer polymethyl acrylate-g-after drying and gather vinyl butyrate.447.96g graft copolymer polymethyl acrylate-g-is gathered vinyl butyrate to be joined in 200.96g methyl alcohol, be warming up to 30 DEG C, add 2.512g sodium hydroxide, alcoholysis 120 minutes, after alcoholysis completes, methanol solvate and by product are sloughed in underpressure distillation, obtain graft copolymer polymethyl acrylate-g-polyvinyl alcohol after drying.228.16g polymethyl acrylate-g-polyvinyl alcohol is joined in 37.6812g water, be warming up to 30 DEG C, add 0.84g sodium hydroxide, be hydrolyzed 120 minutes, be hydrolyzed rear underpressure distillation and sloughed water solvent and by product, after drying, add the polycarboxylate water-reducer solution that 320.25g water obtains 40% mass percent concentration.
Embodiment 2
After the water reducer solution of 40% mass percent concentration obtained in embodiment 1 is deposited 15 days at 6 DEG C, measure its implementation result.
Embodiment 3
First 300g ethanol is joined in reactor, be warming up to 70 DEG C, add 0.06g Virahol, drip 100g ethyl propenoate and the mixed solution of 8.2g Diisopropyl azodicarboxylate 8 hours again, dropping terminate rear continuation isothermal reaction after 5 hours underpressure distillation slough ethanol, obtain polymerisate polyethyl acrylate.Getting the polymerisate polyethyl acrylate that 90g obtains joins in reactor, add 4500g water again, 55.5g sodium laurate, 18.18g n-dodecyl mercaptan, be warming up to 60 DEG C, stir and treat that it mixes in 15 minutes, then the persulfate aqueous solution 8 hours that 1026g vinyl butyrate and 142.8g massfraction are 20% is dripped respectively, dropping terminates rear continuation isothermal reaction 5 hours, be cooled to 30 DEG C, saturated calcium chloride solution breakdown of emulsion is added in the mixed emulsion obtained, use deionized water wash again 4 times, obtain graft copolymer polyethyl acrylate-g-after drying and gather vinyl butyrate.1116g graft copolymer polyethyl acrylate-g-is gathered vinyl butyrate to be joined in 1472g ethanol, be warming up to 40 DEG C, add 16.128g potassium hydroxide, alcoholysis 90 minutes, after alcoholysis completes, alcohol solvent and by product are sloughed in underpressure distillation, obtain graft copolymer polyethyl acrylate-g-polyvinyl alcohol after drying.486g polyethyl acrylate-g-polyvinyl alcohol is joined in 54g water, be warming up to 40 DEG C, add 0.2g potassium hydroxide, be hydrolyzed 90 minutes, be hydrolyzed rear underpressure distillation and sloughed water solvent and by product, after drying, add the polycarboxylate water-reducer solution that 691.2g water obtains 40% mass percent concentration.
Embodiment 4
After the water reducer solution of 40% mass percent concentration obtained in embodiment 3 is deposited 20 days at 6 DEG C, measure its implementation result.
Embodiment 5
First 400g p-Xylol is joined in reactor, be warming up to 100 DEG C, add 5.3146g n-dodecyl mercaptan, drip 100g propyl acrylate and the mixed solution of 2.56g di-t-butyl peroxide 6 hours again, dropping terminate rear continuation isothermal reaction after 3 hours underpressure distillation slough dimethylbenzene, obtain polymerisate polyacrylic acid propyl ester.Getting the polymerisate polyacrylic acid propyl ester that 90g obtains joins in reactor, add 4000g water again, 19.584g sodium laurylsulfonate, 9.076g Thiovanic acid, be warming up to 95 DEG C, stir and treat that it mixes in 30 minutes, then the sodium persulfate aqueous solution 1 hour that 1973g propionate and 75.15g massfraction are 40% is dripped respectively, dropping terminates rear continuation isothermal reaction 5 hours, be cooled to 40 DEG C, saturated liquor alumini chloridi breakdown of emulsion is added in the mixed emulsion obtained, use deionized water wash again 5 times, graft copolymer polyacrylic acid propyl ester-g-polyvinyl proprionate is obtained after drying.2063g graft copolymer polyacrylic acid propyl ester-g-polyvinyl proprionate is joined in 4735.2g propyl alcohol, be warming up to 50 DEG C, add 18.94g sodium hydroxide, alcoholysis 10 minutes, after alcoholysis completes, propanol solvent and by product are sloughed in underpressure distillation, obtain graft copolymer polyacrylic acid propyl ester-g-polyvinyl alcohol after drying.958.12g polyacrylic acid propyl ester-g-polyvinyl alcohol is joined in 71.03g water, be warming up to 50 DEG C, add 0.32g sodium hydroxide, be hydrolyzed 60 minutes, be hydrolyzed rear underpressure distillation and sloughed water solvent and by product, after drying, add the polycarboxylate water-reducer solution that 2158.2g water obtains 30% mass percent concentration.
Embodiment 6
After the water reducer solution of 30% mass percent concentration obtained in embodiment 5 is deposited 30 days at 6 DEG C, measure its implementation result.
Embodiment 7
First 500g ethylene glycol is joined in reactor; be warming up to 130 DEG C; add 3.16g n-dodecyl mercaptan; drip 100g butyl acrylate and the mixed solution of 5.67g dibenzoyl peroxide 1 hour again; dropping terminate rear continuation isothermal reaction after 5 hours underpressure distillation slough ethylene glycol, obtain polymerisate butyl polyacrylate.Getting the polymerisate butyl polyacrylate that 90g obtains joins in reactor, add 3000g water again, 16.2g sodium lauryl sulphate, 14.84g thiohydracrylic acid, be warming up to 80 DEG C, stir and treat that it mixes in 20 minutes, then the ammonium persulfate aqueous solution 6 hours that 1406g propionate and 49.88g massfraction are 50% is dripped respectively, dropping terminates rear continuation isothermal reaction 2 hours, be cooled to 25 DEG C, saturated calcium chloride solution breakdown of emulsion is added in the mixed emulsion obtained, use deionized water wash again 5 times, graft copolymer butyl polyacrylate-g-polyvinyl proprionate is obtained after drying.1496g graft copolymer butyl polyacrylate-g-polyvinyl proprionate is joined in 4480g methyl alcohol, be warming up to 60 DEG C, add 7.87g potassium hydroxide, alcoholysis 30 minutes, after alcoholysis completes, methanol solvate and by product are sloughed in underpressure distillation, obtain graft copolymer butyl polyacrylate-g-polyvinyl alcohol after drying.708.64g butyl polyacrylate-g-polyvinyl alcohol is joined in 75.924g water, be warming up to 60 DEG C, add 0.945g potassium hydroxide, be hydrolyzed 20 minutes, be hydrolyzed rear underpressure distillation and sloughed water solvent and by product, after drying, add the polycarboxylate water-reducer solution that 1561.1g water obtains 30% mass percent concentration.
Embodiment 8
After the water reducer solution of 30% mass percent concentration obtained in embodiment 7 is deposited 15 days at 6 DEG C, measure its implementation result.
Embodiment 9
First 1000g toluene is joined in reactor, be warming up to 90 DEG C, add the different monooctyl ester of 1.5347g3-thiohydracrylic acid, drip 100g amyl acrylate and the mixed solution of 2.53g tertbutyl peroxide 7 hours again, dropping terminate rear continuation isothermal reaction after 4 hours underpressure distillation slough toluene, obtain polymerisate polyacrylic acid pentyl ester.Getting the polymerisate polyacrylic acid pentyl ester that 90g obtains joins in reactor, add 5000g water again, 1.7g sodium stearate, 5.76g n-dodecyl mercaptan, be warming up to 95 DEG C, stir and treat that it mixes in 30 minutes, then the ammonium persulfate aqueous solution 5 hours that 2453.58g vinyl-acetic ester and 72.28g massfraction are 40% is dripped respectively, dropping terminates rear continuation isothermal reaction 3 hours, be cooled to 25 DEG C, saturated liquor alumini chloridi breakdown of emulsion is added in the mixed emulsion obtained, use deionized water wash again 4 times, graft copolymer polyacrylic acid pentyl ester-g-polyvinyl acetate is obtained after drying.2543.58g graft copolymer polyacrylic acid pentyl ester-g-polyvinyl acetate is joined in 7874.28g ethanol, be warming up to 70 DEG C, add 13.69g sodium hydroxide, alcoholysis 30 minutes, after alcoholysis completes, alcohol solvent and by product are sloughed in underpressure distillation, obtain graft copolymer polyacrylic acid pentyl ester-g-polyvinyl alcohol after drying.1345.32g polyacrylic acid pentyl ester-g-polyvinyl alcohol is joined in 114.12g water, be warming up to 70 DEG C, add 1.52g sodium hydroxide, be hydrolyzed 10 minutes, be hydrolyzed rear underpressure distillation and sloughed water solvent and by product, after drying, add the polycarboxylate water-reducer solution that 5203.88g water obtains 20% mass percent concentration.
Embodiment 10
After the water reducer solution of 20% mass percent concentration obtained in embodiment 9 is deposited 30 days at 6 DEG C, measure its implementation result.
Embodiment 11
First 500g 200# solvent oil is joined in reactor, be warming up to 105 DEG C, add the different monooctyl ester of 0.436g3-thiohydracrylic acid, drip 100g butyl acrylate and the mixed solution of 4.55g peroxidized t-butyl perbenzoate 5 hours again, dropping terminate rear continuation isothermal reaction after 3 hours underpressure distillation slough 200# solvent oil, obtain polymerisate butyl polyacrylate.Getting the polymerisate butyl polyacrylate that 90g obtains joins in reactor, add 3600g water again, 2.4337g sodium stearate, 12.65g Virahol, be warming up to 80 DEG C, stir and treat that it mixes in 25 minutes, then the ammonium persulfate aqueous solution 6 hours that 1813.74g vinyl-acetic ester and 63.84g massfraction are 50% is dripped respectively, dropping terminates rear continuation isothermal reaction 3 hours, be cooled to 30 DEG C, saturated liquor alumini chloridi breakdown of emulsion is added in the mixed emulsion obtained, use deionized water wash again 3 times, graft copolymer butyl polyacrylate-g-polyvinyl acetate is obtained after drying.1903.74g graft copolymer butyl polyacrylate-g-polyvinyl acetate is joined in 2530.8g propyl alcohol, be warming up to 45 DEG C, add 11.81g potassium hydroxide, alcoholysis 45 minutes, after alcoholysis completes, propanol solvent and by product are sloughed in underpressure distillation, obtain graft copolymer butyl polyacrylate-g-polyvinyl alcohol after drying.1017.96g butyl polyacrylate-g-polyvinyl alcohol is joined in 101.23g water, be warming up to 50 DEG C, add 2.52g potassium hydroxide, be hydrolyzed 60 minutes, be hydrolyzed rear underpressure distillation and sloughed water solvent and by product, after drying, add the polycarboxylate water-reducer solution that 3914.28g water obtains 20% mass percent concentration.
Embodiment 12
After the water reducer solution of 20% mass percent concentration obtained in embodiment 11 is deposited 15 days at 6 DEG C, measure its implementation result.
Implementation result:
1. flowing degree of net paste of cement
For investigating the polycarboxylate water-reducer solution of the present invention's synthesis to the mobility action effect of different cement, measuring under identical volume each embodiment to the paste flowing degree of different cement type.Test is undertaken by GB/T8077-2012 " Methods for testing uniformity of concrete admixture ", W/C=0.35, and volume is the solid volume of folding.Test-results is in table 1.
Table 1 pulp flowage results of property
As can be seen from Table 1, the polycarboxylate water-reducer solution of the inventive method synthesis, under the water cement ratio 0.35 and the folding of 2.0% consolidate volume, all can show excellent dispersive ability and cement adaptability.
2. other volume paste flowing degree
The feature of this product is that cement paste still can keep higher dispersing property in other volume (1.2%-1.8%) situation.Test is undertaken by GB/T8077-2012 " Methods for testing uniformity of concrete admixture ", cement selection reference cement, W/C=0.35.Test-results is in table 2.
Pulp flowage results of property under table 2 low-dosage
As can be seen from Table 2, the polycarboxylate water-reducer solution that the inventive method is synthesized all has clean preferably slurry initially and maintenance mobility result under other volume.
3. concrete slump and divergence
The divergence that each embodiment of test determination shows in concrete system and the slump and retention.Test-results is in table 3.
Table 3 concrete flowability energy result
As can be seen from Table 3, the polycarboxylate water-reducer solution of the inventive method synthesis all can show excellent divergence and the hold facility of the slump in concrete system.
Claims (1)
1. acrylic polymer graft copolymerization vinyl fatty ester prepares a method for polycarboxylate water-reducer, it is characterized in that, as follows by the condition and step of being first polymerized the method synthesis polycarboxylate water-reducer of alcoholysis and hydrolysis after grafting again:
(1) polyreaction: first organic solvent is joined in reactor, be warming up to 60-130 DEG C, add molecular weight regulator, drip acrylate and the mixed solution 1-10 hour of initiator again, dropping terminates rear continuation isothermal reaction 0.5-5 hour, organic solvent is sloughed in underpressure distillation, obtains polymerisate polyacrylic ester;
(2) graft copolymerization: the polymerisate obtained in step (1) is joined in reactor, add water, emulsifying agent, molecular weight regulator successively again, be warming up to 50-95 DEG C, stir and treat that it mixes in 10-30 minute, then dropping vinyl fatty ester and massfraction are the initiator solution 1-10 hour of 5-50% respectively, dropping terminates rear continuation isothermal reaction 1-5 hour, be cooled to 25-40 DEG C, inorganic salt saturated solution breakdown of emulsion is added in the mixed emulsion obtained, use deionized water wash 2-5 time again, obtain polymerisate;
(3) alcoholysis reaction: the polymerisate obtained in step (2) is joined in alcoholic solvent, be warming up to 30-70 DEG C, add mineral alkali, alcoholysis 10-120 minute, after alcoholysis completes, alcoholic solvent and by product are sloughed in underpressure distillation, obtain polyacrylic ester-g-polyvinyl alcohol after drying;
(4) hydrolysis reaction: polymkeric substance step (3) obtained mixes with hydrolysis water used, be warming up to 30-70 DEG C, add mineral alkali, hydrolysis 10-120 minute, be hydrolyzed rear underpressure distillation and sloughed water solvent and by product, after drying, add the polycarboxylate water-reducer solution that aqueous solvent obtains desired concn;
Wherein, organic solvent used in the polyreaction described in step (1) is methyl alcohol, ethanol, p-Xylol, 200# solvent oil, ethylene glycol, toluene or hexanaphthene, and the mass ratio of consumption and acrylate is 2-10:1; Molecular weight regulator described in step (1) is Virahol, n-dodecyl mercaptan or the different monooctyl ester of 3-thiohydracrylic acid, and the mol ratio of consumption and acrylate is 0.001-0.05:1; Acrylate described in step (1) is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate or amyl acrylate; Initiator described in step (1) is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, tertbutyl peroxide, peroxidized t-butyl perbenzoate or di-t-butyl peroxide, and the mol ratio of consumption and acrylate is 0.001-0.05:1;
The consumption adding water described in step (2) and the polyacrylic ester mass ratio described in step (1) are 5-50:1; Emulsifying agent described in step (2) is sodium laurate, sodium laurylsulfonate, sodium lauryl sulphate or sodium stearate, and consumption is 0.00002-0.004:1 with the mol ratio adding water; Molecular weight regulator described in step (2) is n-dodecyl mercaptan, Virahol, Thiovanic acid or thiohydracrylic acid, and consumption and vinyl fatty ester mol ratio are 0.001-0.05:1; Vinyl fatty ester described in step (2) is vinyl-acetic ester, propionate or vinyl butyrate, and the mol ratio of consumption and the acrylate described in step (1) is 3-45:1; The solute of the initiator solution described in step (2) is Potassium Persulphate, Sodium Persulfate or ammonium persulphate, and the mol ratio of solute consumption and the acrylate described in step (1) is 0.1-0.2:1; Inorganic salt saturated solution described in step (2) is saturated nacl aqueous solution, saturated calcium chloride solution or saturated liquor alumini chloridi;
Alcohol described in step (3) is methyl alcohol, ethanol or propyl alcohol, and the mol ratio of consumption and the vinyl fatty ester described in step (2) is 2-5:1; Mineral alkali described in step (3) is sodium hydroxide or potassium hydroxide, and the mol ratio of consumption and alcohol is 0.001-0.01:1;
The consumption of the hydrolysis water used described in step (4) and the mol ratio of the acrylate described in step (1) are 2-10:1; Mineral alkali described in step (4) is sodium hydroxide or potassium hydroxide, and consumption is 0.001-0.01:1 with the mol ratio of hydrolysis water used.
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| US14/829,505 US9453097B2 (en) | 2015-02-15 | 2015-08-18 | Method for preparation of polycarboxylate superplasticizer by graft copolymerization of fatty acid vinyl ester onto acrylate polymer |
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